Selectivity in Methanol Oxidation as Studied on Model Systems Involving Vanadium Oxides

Oxidation catalysts are modeled by oxide single crystals, thin oxide films, as well as supported oxide nanoparticles. We characterize the surface of those materials using a variety of surface sensitive techniques including scanning tunneling microscopy and spectroscopy, photoelectron spectroscopy, infrared spectroscopy, and thermal desorption spectroscopy. We find temperature dependent structural transformations from V₂O₅(001) to V₂O₃(0001) via V₆O₁₃(001). V₂O₃(0001) is found to be vanadyl terminated in an oxygen ambient and it loses the vanadyl termination after electron bombardment. It is shown that the concentration of vanadyl groups controls the selectivity of the methanol oxy-dehydrogenation towards formaldehyde. A proposal for the mechanism is made. The results on single crystalline thin films are compared with similar measurements on deposited vanadia nanoparticles. The experimental results are correlated with theoretical calculations and models.     

Preparation of Phase-Pure M1 MoVTeNb Oxide Catalysts by Hydrothermal Synthesis—Influence of Reaction Parameters on Structure and Morphology

This work presents a detailed investigation of the preparation of MoVTeNbO _x catalysts by hydrothermal synthesis. Phase-pure synthesis of M1 has been achieved applying the metals in a molar ratio Mo/V/Te/Nb = 1/0.25/0.23/0.12. Raman, UV/Vis spectroscopy, and SEM/EDX analysis show that the elements are inhomogeneously distributed in the initial suspension that is formed after mixing the metal salts in an aqueous medium. Iso- and heteropoly anions of molybdenum, free telluric acid as well as supra-molecular polyoxometalate clusters are observed in the solution, whereas all metals have been found in the precipitate. Complete rearrangement of molecular building blocks under hydrothermal conditions is essential for formation of phase-pure materials. Optimized synthesis conditions with respect to temperature and time result in the formation of a precursor consisting of nano-structured M1 characterized by an extended periodic organization in the [001] direction and a fairly homogeneous distribution of the elements. Residual ammonium containing supra-molecular species in the precursor result in the formation of phase mixtures during the subsequent crystallization by heat treatment in inert gas. Phase-pure M1 exhibits a distinct degree of flexibility with respect to the chemical composition that becomes obvious by incorporating Nb not exclusively into pentagonal bi-pyramidal units, but also into octahedral coordinated positions as shown by EXAFS. Anisotropic growth of the needle-like M1 crystals has been observed during the final heat treatment performed at 873–923 K in inert atmosphere disclosing a potential method to control the catalytic properties of MoVTeNbO _x catalysts.     

Efficient reconstruction from non-uniform point sets

We propose a method for non-uniform reconstruction of 3D scalar data. Typically, radial basis functions, trigonometric polynomials or shift-invariant functions are used in the functional approximation of 3D data. We adopt a variational approach for the reconstruction and rendering of 3D data. The principle idea is based on data fitting via thin-plate splines. An approximation by B-splines offers more compact support for fast reconstruction. We adopt this method for large datasets by introducing a block-based reconstruction approach. This makes the method practical for large datasets. Our reconstruction will be smooth across blocks. We give reconstruction measurements as error estimations based on different parameter settings and also an insight on the computational effort. We show that the block size used in reconstruction has a negligible effect on the reconstruction error. Finally we show rendering results to emphasize the quality of this 3D reconstruction technique.     

Co-Channel Operation of Macro- and Femtocells in a Hierarchical Cell Structure

In this paper, the feasibility of user-deployed femtocells in the same frequency band as an existing macrocell network is investigated. Key requirements for co-channel operation of femtocells such as auto-configuration and public access are discussed. Methods for femtocell power auto-configuration that ensure a constant cell radius in the downlink, and a low pre-definable interference impact on co-channel macrocells in the uplink are proposed. The theoretical performance of randomly deployed femtocells in such a hierarchical cell structure and the resulting impact on existing co-channel macrocells is analysed for a cellular UMTS network using system level simulations.     

Atomic force microscopy on polymers and polymer related compounds

Summary Surface morphology and molecular arrangement have been recorded by atomic force microscopy (AFM) on polytetrafluoroethylene (PTFE) and on polycarbonate (PC) films. In a thin layer of PTFE deposited by rubbing polymer on hot glass substrate unidirectional orientation of polymer has been revealed. Individual polymer chains have been visualized. An interchain distance of .53 nm and several periodicities along the chain contours have been found-.44 nm, .62 nm and .82 nm-in accordance with a 13/6 helix.The monitoring of surface changes during thermal treatment of amorphous-bis-phenol A-PC film has been realized by AFM. Different types of surface morphology were revealed. Spherulites are formed during polymer crystallization. In most cases, however, numerous nanocrystallites appeared after thermal treatment. On their surfaces well-ordered atomic scale AFM images have been received. The arrangement of AFM patterns can be characterized by periodicities of .50 nm and .52 nm in the orthogonal directions. Polycarbonate oligomers-as the product of surface degradation-effectively might form the observed nanocrystallites.Prof. Dr. G. Zachmann zum 60. Geburtstag herzlichst gewidmetThese results were given by us first in a lecture in Baltimore, at the 5th ISPAC Symposium on May 31, 1991, and in a lecture in Santa Barbara, at the Nanoscope Users Meeting on June 25, 1991     

Zur Reaktivität von Tanninen in Abhängigkeit vom Kambialalter

Ohne Zusammenfassung     

A General Reliable Quadratic Form: An Extension of Affine Arithmetic

In this article, a new extension of affine arithmetic is introduced. This technique is based on a quadratic form named general quadratic form. We focus here on the computation of reliable bounds of a function over a hypercube by using this new tool. Some properties of first quadratic functions and then polynomial ones are reported. In order to show the efficiency of such a method, ten polynomial global optimization problems are presented and solved by using an interval branch-and-bound based algorithm. The work of the first author was also supported by the Laboratoire de Mathématiques Appliquées CNRS–FRE 2570, Université de Pau et des Pays de l'Adour, France, and by the Laboratoire d'Electrotechnique et d'Electronique Industrielle CNRS–UMR5828, Group EM³, INPT–ENSEEIHT.     

Heat transfer and pressure drop in a new type of corrugated channels

An experimental investigation of heat transfer and pressure drop from a new type of corrugated channels is presented. The investigation has been carried out for Reynolds numbers in the range of $\text{800 <}\text{Re}\text{< 5000}$ for one corrugated and one smooth channel. It is found that the heat transfer from the corrugated channel is up to 3.5 times higher than for the smooth one. The pressure drop is however large (5 – 6 times the value of a smooth channel) and it is suggested that the corrugation height and length should be altered in order to balance the increases in heat transfer and pressure drop.